Cellulosic spinning solution



Patented Mar. 3, 1942 CELLULOSIC SPINNING SOLUTION Thomas A. Printon, South Orange, N. J., assignor to National Oil Products Company, Harrison, N. J., a corporation of New Jersey No Drawing. Application May 4, 1933, Serial No. 205,987

7 Claims. This invention relates in general to the manufacture of non-fibrous cellulosic materials, and

in particular to a composition and process of producing delustered non-fibrous cellulosic materials and to correlated improvements in the delustered materials thus produced.

The non-fibrous cellulosic materials produced according to the processes employed in the early days of this industry were endowed with a high gloss and lustre. At the outset this result was highly desirable, but as time went on high lustre became objectionable especially in the artificial silk field due to the fact that fabrics produced from lustrous rayon displayed an artificial and coarse appearance. Since this early era many proposals have been offered in an attempt to produce cellulosic yarns having a subdued lustre. One of the earliest proposals for effecting a dull lustre viscose yarn was to retain the sulfur par-' ticles in the yarn by omitting the conventional desulfurizing step during its manufacture. While the retained sulfur particles imparted a decreased lustre to the freshly prepared yarn, it was not permanent and after a time exhibited an unattractive bloom. Further proposals have included the incorporation of various pigments, hydrocarbons, oils, fats, waxes and other agents into viscose, cuprammonium and like cellulosic solutions before extrusion thereof. In many instances the use of various emulsifying agents including, inter alia, sulfonated fatty materials,

has been'resorted to in an attempt to obtain' satisfactory dispersion of such delustrants in cellulosic solutions. While the use of sulfonated fatty materials as emulsifiers for delustrants is commercially feasible in view of their low cost, ease of handling, etc., their use for this purpose has presented many diflicult problems with commensurate disadvantages. Sulfonation products of fatty animal and vegetable materials, such as fatty acids, fatty oils, fats, waxes and their derivatives as now produced commercially, contain large quantities of moisture and inorganic salts, which it has been found are the prime causes of the aforementioned problems and resulting disadvantages. The moisture or water present in normal sulfonated products result, in part, from the reaction effected during the sulfonation step and in part from that introduced during the washing, panning, neutralizing and the other conventional steps employed in the preparation of these products. The inorganic salts are introduced during the same steps and especially during the neutralizing step.

It has been found that the relatively high moisture and inorganic salt content of sulfonated products of the aforementioned type is undesirable and detrimental for various reasons. The high water content of these products greatly reduces their blending action with non-sulfonated oils, fat, waxes and other delustrants with which they are incorporated for providing the desired emulsifying properties. The inorganic salt content of the sulfonated products greatly reduces the stability of emulsions produced by use of such products, thereby deleteriously affecting the uniformity of the delustering effects in the cellulosic materials thus produced.

The general object of the present invention is to obviate the foregoing and other disadvantages.

An additional object of the invention is to provide an improved spinning composition for producing cellulosic bodies presenting enhanced delustered effects.

Another object of the invention is to provide delustered non-fibrous cellulosic yarns of improved appearance.

A specific object of the invention is to provide an improved delustering composition adapted for addition to cellulosic solutions.

Other objects of the invention will in part be obvious and will in part appear hereinafter.

It has now been discovered that the foregoing and other objects may be realized by the use of substantially anhydrous and salt-free sulfonated fatty materials in the delustering of cellulosic materials. According to the invention a composition comprising a substantially anhydrous and salt-free sulfonated fatty material and an oily substance is incorporated into a cellulosic solution prior to extrusion thereof. The oily substance, which is dispersed in the cellulosic solution by means of the aforementioned sulfonated material, may comprise any suitable substance, such as mineral, vegetable or animal fat, oil or wax and/or suitable derivative thereof which will impart a delustering effect to the cellulosic product produced.

The invention accordingly comprises the several steps and relation of one or more of such steps with respect to each of the others, and a composition of matter possessing the characteristics, properties and relation of components all of which will be exemplified in the following detailed disclosure, and the scope of the invention will be indicated in the claims.

The substantially anhydrous and salt-free sulfonated products referred to and employed in the present invention may be produced accord- ,L. J. Mosch and E. T. Woods.

' bone fat, horse 'fat,

ing to any suitable process which will result in a sulfonated product that is substantially free from water and inorganic salts. These products are, however, preferably prepared according to the processes disclosed in any of the following copending patent applications, Serial No. 77,761, filed May 4, 1936, applicant being Karl T. Steik; Serial No. 160,270, filed August 21, 1937, applicant being Karl T. Steik; and Serial No. 197,858, 'filed March 24, 1938, applicants being R. Kapp,

The process according to the first two applications comprises sulfonating a fatty material such as fatty acids, fatty oil, fatty waxes and fatty derivatives in the usual manner and then taking up the crude sulfonation mass in a substantially anhydrous organic solvent for the mass and neutralizing the mass by meansof a concentrated aqueous solution of an alkali or alkali dissolved in an organic solvent. The inorganic salts formed during neutralization, as well as any salt that might be present in the mass, precipitate out from the sulfonated product. The volume of the solvent used must be 'at least equal to the volume of the mass and preferably two to four times that quantity ofsolvent is used. The precipitated salts are removed from the sulfonated mass by filtration, centrifuging, decanting or otherwise. After the salts are removed, the sulfonated mass is subjected to distillation, preferably under vacuum, to drive off the solvent and any remaimng water. The latter cited application discloses a process wherein the sulfonated material is washed, neutralized and panned in the usual manner, after which it is' partially dehydrated under reduced pressure at a relatively'low temperature which will not deleteriously affect the sulfonated material. After the greater part of the water has been removed, the mass is 'taken up in solvent, whereupon the salts are precipitated out. The mass is then filtered to remove the inorganic salts and the solvent and residual water are removed by distillation. The substantially anhydrous and salt-free sulfonated oils and like products produced in accordance with the foregoing processes. are characterized by having a moisture content of not more than 3.0% by weight and an inorganic salt content of not more than 0.2% by weight. Suitable fatty materials which may be sulfonated and treated according to these processes include the general class consisting of animal, vegetable and marine oils, fats and their respective fatty acids and fatty esters, specific examples of which include, inter alia, oils, fats and waxes, such as castor, com,' cottonseed, linseed, olive, palm, peanut, sunflower, rape ,seed, teaseed, rice bran, chaulmoogra, tomato seed, sesame, soya bean, cacao butter, Chinese tallow, cod, herring, menhaden, porpoise, seal, salmon, sardine, shark, sperm, whale, tuna, neats-foot, beef tallow, mutton tallow, wool grease, etc., as well as the corresponding acids of these products. Suitable derivatives of theseor other fatty materials may also be used as alkyl, glycol or glyceryl esters of the higher fatty acids.

The substantially anhydrous and inorganic, salt-free sulfonated products derived from the foregoing processes exhibit marked and distinct improvements over the prior known sulfonated products, especially with respect to their blending and emulsifying actions when combined with delusterants. Ordinary sulfonated oils available on the market contain from about 10% to 30% or more water and varying quantities of inoramides, etc.

ganic salts ranging from about one percent and up. For example, in preparing delustering compositions containing a mineral oil, it was necessary heretofore to admix 20 to 25 parts of an ordinary sulfonated oil of the aforementioned type with 60 to 70 parts of mineral oil, after which various stabilizing and blending agents, such as alkalies, fatty acids, organic solvents, etc. were added to bring about a dispersible product. These extraneous agents were found to deleteriously affect the cellulosic spinning solutions as Well as the products produced therefrom. It has now been found that an improved, readily dispersible, blended, delustering composition may be produced by merely admixing a suitable quantity of a substantially anhydrous and salt-free sulfonated oil with the desired delustering agent.

In preparing the delustering composition of the invention, a substantially anhydrous and salt-free sulfonated fatty material may be blended with a suitable water-immiscible substance adapted for delustering cellulosic materials, such as animal, vegetable and/or mineral oils, fats and waxes, fatty acids, fatty alcohols, fatty Other suitable delusterants may also be used, such as chlorinated diphenyl, halogenated oils, fats, waxes and resins. Substances of the aforementioned type are characterized by being oily or waxy in nature and the expression an oily delustering agent is used herein to generically connote such a class of substances. Inorganic pigments such as titanium dioxide and the like may be used in conjunction with the foregoing delustering compositions. While any of the above delustering agents may be used in the composition of the invention, the use of mineral oils, jellies or waxes, such as paraffin oil,

petrolatum, paraflin wax, etc. are highly preferred. Thebroad water-dispersible composition comprising a water-immiscible oil blended with the aforementioned type of sulfonated fatty material is disclosed and claimed in application Serial No. 205,984, filed on May 4, 1938, by Roland Kapp and Karl T. Steik.

The quantity of substantially anhydrous and salt-free sulfonated material used may be varied within wide limits, depending upon the delusterant to be used and the particular cellulosic solution to be treated. It has been found, however, that about 2.5% to 15% of the sulfonated material, based on the weight of the delustering agent, is suitable for all practical purposes. The quantity of the dispersible delustering composition of the invention to be added to viscose, cu'prammonium and like cellulosic solutions, may be varied according to the results desired; a range of about .05 to 10% based on the weight of the cellulose content in the solution is recommended.

For a fuller understanding of the nature and objects of the invention, reference should be had to the following examples which are given merely to illustrate further the invention and are not to be construed in a limiting sensez Example I Six parts by weight of substantially anhydrous and salt-free sulfonated sperm oil containing not more than 3.0% moisture and 0.2%. inorganic salts is admixed with 94 parts by weight of a light-colored mineral oil. Twenty parts of this dispersible composition are dispersed in 5,000 parts of a viscose solution containing about 7% more or lessof cellulose.

Upon extrusion of the foregoing solution into filaments, films, pellicles, tubes, rods, etc., the

resulting product displays an enhanced and uniform delustered or matte appearance.

Example II Eight parts by weight of substantially anhydrous and salt-free sulfonated olive oil containing not more than 3.0% moisture and 0.2% inorganic salts and 92 parts by weight of paraflin oil are blended together by stirring. Twentyfive parts of the above dispersible mixture is dispersed in 5000 parts by weight of a cuprammonium cellulose solution.

The present invention is adapted for practice in the production of non-fibrous cellulosic prodi forming materials incorporated therein, such as casein, synthetic resins, rubber, latex, etc.

The advantages of the delustering composition of the invention are many and include, among others, (a) uniform delustering, (b) even dispersion of delustrant, (c) uniform size of the delustering particles, (d) no discoloration of the resulting products (e) an increase in strength of the products with respect to other delustered products and (f) a stable dispersion of the delustrant in the cellulosic solution is obtained.

Since certain changes in carrying out the above process and certain modifications in the composition which embody the invention may be made without departing from its scope, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.

.It is also to be understood that the following claims are intended to cover all the generic and specific features of the invention herein described and all statements of the scope of the invention, which as a matter of language, might be said to fall therebetween; and that they arelntended to be inclusive in scope and not exclusive, in that if desired, other materials may be added to my novel composition of matter herein claimed without departing from the spirltof the invention. Particularly it is to be understood that in said claims, ingredients or components recited in the singular are intended to include compatible mixtures of said ingredients wherever the sense per- I mits.

Having described my invention what I claim as new and desire to secure by Letters Patent is:

1. A spinning solution for the manufacture oflow lustre products comprising an aqueous cellulosic solution having dispersed therein a mixture of a, sulfonation product of a material selected from the class consisting of animal, vegetable and marine oils, fats and their respective fatty acids and fatty esters, the sulfonation product being characterized by having a moisture content of not more than 3.0% and an inorganic salt content of not more than 0.2% by weight and an oily delustering agent, the quantity of said sulfonation product based on the weight of the delustering agent being between 2.5% and 15% in said mixture.

2. A spinning solution for the manufacture of low lustre products comprising viscose having dispersed therein a mixture of a sulfonation product of a material selected from the class consisting of animal, vegetable and marine oils, fats and their respective fatty acids and fatty esters, the sulfonation product being characterized by having a moisture content of not more than 3.0% and an inorganic saltcontent of not more than 0.2% by weight and an oily delustering agent, the quantity of said sulfonation product based on the weight of the delustering agent being between 2.5% and 15% in said mixture.

3. A spinning solution for the manufacture of low lustre products comprising a cuprammonium solution of cellulose having dispersed therein a.

mixture of a sulfonation product of a material selected from the class consisting of animal, vegetable and marine oils, fats and their respective fatty acids and fatty esters, the sulfonation product being characterized by having a moisture content of not more than 3.0% and an inorganic salt content of not more than 0.2% by weight and an oily delustering agent, the quantity of said sulfonation product based on the weight of the delustering agent being between 2.5% and 15% in said mixture.

4. A spinning solution for the monufacture of low lustre products comprising viscose having dispersed therein a mixture of a sulfonation product of a material selected from the class consisting of animal, vegetable and marine oils, fats and their respective fatty acids and fatty esters, the sulfonation product being characterized by having a moisture content of not more than 3.0% and an inorganic salt content of not more than 0.2% by weight and a mineral oil, the quantity of said sulfonation product based on the weight of the delustering agent being between 2.5% and 15% in said mixture.

5. A spinning solution for the manufacture of low lustre products comprising a cuprammonium solution of cellulose having dispersed therein a mixture of a sulfonation product of a material selected from the class consisting of animal, vegetable and marine oils, fats and their respective fatty acids and fatty esters, the sulfonation product being characterized by having a moisture content of not more than 3.0% and an inorganic salt content of not more than 0.2% by Weight and a mineral oil, the quantity of said sulfonation product based on the weight of the delustering agent being between 2.5% and 15% in saidmixture.

'6. A spinning solution for the manufacture of low lustre products comprising viscose having dispersed therein a mixture of sulionated sperm oil containing not more than 3.0% moisture and not more than 0.2% inorganic salts by weight and a mineral oil, the quantity of said sulfonation product based on the weight of the delustering agent being between 2.5% and 15% in said mix.- ture.

'7. A spinning solution for the manufacture of low lustre products comprising cuprammonium solution of cellulose having dispersed therein a 

